Disazo dyestuffs



UNITED "STATES PAT E OFFICE I DISAZO DYEISTUFFS Hans Ischer,

Basel, switzerlaniassignor to Sandcz A. G., Basel, Switzerland, a Swiss firm 229,529; In Switzerland June 27,

Drawing. Application June 1,-1951, s 1; ia1 No;

doma ns; (01. 260 -187) Th present invention relates to a new group of valuable disazo dyestuffs, the individual members of which are obtained by coupling an appropriate diazotizedaminoazo dyestufi' which'correa sponds to the formula v HOaS wherein R represents an aromatic radical .of the benzene 'or naphthalene series which, in ortho position to the azo group, bears a substituent which is capable of metal complex formation, X stands for H or SOsH, one Y stands for CH3, and

th other Y stands for NHz, with an amino-hydroxy-naphthalene-sulfonic acid which corresponds to the formula wherein the naphthalene nucleus may carry a further SOaH group.

The dyestuffs (I) which serve as startlng compounds for the preparationoi the new dyestuffs 6 -nitrobenzene "-4- sulfonic may themselves be obtained, for example, "by c Ouwith an aminobenaovl aminonaphthol sulfonic acidwhlch corresponds to the formula I wherein X and Y have the afore-indicated significances. I I

' Suitable amines for this purpose are primarily those of the benzene and naphthalene series, such for example as 1-methoxy-2-aminobenzene- 4-sulfqnic acid, l-methoxy-2-amino-4-methy1;- benzene, 1-methoxy-2-amino-5-nitrobenzene, ,1- methoxy-2-amino-4-chlorobenzene, '1 mthoxyz-amino-i-sulfonic acid amide, 'l hyd'roxyi-2- aminobenzene, l hydroXy 2 aminobenzene-isulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid amide, 1=hydrogy-2-aminobenzene-r4-' s'ulfonic'j acid anilide, .1-hydroxy-2-aminobeniene 4"-' sulfonic acid (4'-hydroXy 3" carboxy-' anilide) l-hydroxy-2-amino 6 chlorobenzenee l sulfonic acid, 1-hydroxy-2- amino-4-chlorobenz'ene 6 -'sulfonic acid,"1-hydroxy-2-amino 4-ni trobenz8ne-6-sulfonic' acid, 'l-hydroxy-Z-aniinoacid, l-hydroxy-2- amino-3,6-dichlorobenzene 4 sulfonic acid, 1'- hydroxy-Z-amino4-nitrobenzene, 1-hydroxy-2- amino-5-nitrobenzene, I-hydroxy-Zamino-34,6- trichloroben'zene, 2-amino-benzenel carboirylic acid, 1-carboxy-2-aminobenzene-4-isulfonic acid, 1-carboxy-2-aminobenzene 5 sulfonic acid, v 1-.- carboxy-2-aminoben'zene 4 carboxylic acid, 1- carboxy-Z aminobena'ene-5 carboxylic acid, 2'- amino-phen'oxyacetic acid, 4 -chloro-2-aminophenoxyacetic acid, 4'-methyl 2' amino phenox'yacetic acid, 4' sulfamido 2' amino-phenoxyacetic acid, l-methoxy 2-'- aminonaphthalene, 2-methoxy-l-aminonap-hthalene, 2-methi oxy 1- aminonaphthalene 6 sulfonic acid, 1- amino-2-hydroxynaphthalene-4-sulfonic acid, 1- mino=2 hydroxy-G-nitronaphthalene-4-sulfonilc acid, 3-aminonaphthalene- 2-carboxylic acid, etc,

Suitable coupling components for use in preparingthefst'arting dyestuffsiI) comprise, for

example, 2- (3'-methyl-4' -aminobenzoyl) -aminohydroxynaphthalene -7 sulfonic acid, 2 (4'- methyl 3 aminobenzoyl) amino 5 hydroxynaphthalene-7-sulfonic acid, 2'-(3'-methyl- 4' aminobenzoyl) amino 5 hydroxy naphthalene 1,7 disulfonic acid, 2 (4 methyl- 3 aminobenzoyl) amino -5- hydroxynaphthalene-l,7-disulfonic acid, etc.

The further diazotization of the thus-obtained monoazo dyestufis, corresponding to formula (I) supra, is advantageously carried out in indirect manner by adding the necessary quantity of sodium nitrite to a neutral or weakly alkaline suspension of the dyestufi and then acidifying with hydrochloric acid, or by running the nitrite-containing suspension into hydrochloric acid. The resultant diazo compounds are then, according to the invention, coupled with acylamino-hydroxy naphthalene-sulfonic acids. Suitable coupling components for this purpose, according to the invention, include for example 2-acetylamino-5- hydroxynaphthalene 7 sulfonic acid, 2 carbethoxy 5 hydroxynaphthalene '7 sulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7- sulfonic acid, 2-benzoylamino-5-hydroxynaphthalene 1,7 disulfonic acid, 2 (2 carboxybenzoyl) amino 5 hydroxynaphthalene 7- sulfonic acid, 2-(2'-chlorobenzoyl) -amino-5-hydroxynaphthalene-7-sulfonic acid, 2-cinnamoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- cinnamoylamino 5 hydroxynaphthalen 1,7- disulfonic acid, 2 (4 benzoylaminobenzoyD- amino 5 hydroxynaphthalene 1,7 disulfonic acid, 2 benzoylamino 8 hydroxynaphthalene- 6-sulfonic acid, 2 cinnamoylamino 8 hydroxynaphthalene 6 sulfonic acid, 1 benzoylamino 8 hydroxynaphthalene 6 sulfonic acid, 1 cinnamoylamino 8 hydroxynaphthalene-fi-sulfo'nic acid, 1-cin'namoy1amino-8-hydroxynaphthalene-4,6-disulfonic acid, l-benzoylamino 8 hydroxynaphthalene 4,6 disulfonic acid, 1-benzoy1amino-5-hydroxynaphthalene-7- sulfonic acid, 2-(4-arninobenzoyl) -amino-5-hydroxynaphthalene-7-sulfonic acid, 2- (3"-amino-' benzoyl) amino 5 hydroxynaphthalene 7'- sulfonic acid, 2'-(4-aminobenzoyl) -amino-5-hydrox'yn'aplithalene 1,7 disulfonic acid, 2"- (4- aininobenzo'yl) amino 8" hydroxynaphthalene 6 sulfonic acid, 2 (W-methyl 4'- aminoben'zoyl) amino 5 hydroxynaphthalen 7 sulfor'iic' acid, 2 (4 methyl-3'- amin'obenzoyl') amino 5 hydro'x'ynaphthalene 'I sulfonic acid, 2 (3 methyl 4- aminobenzoyl) amino 5- hydroxynaphtha- 1ene-1,7-di'sulfonic acid, etc.

The new disazo dyestuffs thus obtained may therefore be characterized by the formula wherein R1 is the radical of a compound of the benzene or naphthalene series bearing in orthoposition to the azo group a substituent capable of forming metal complexes, R2 stands for the radical of one of the coupling'comp'onents:

2 (3' methyl 4 aminobenzoyl); amino- 5-hydroxynaphthalene-7-sulfonic acid,

2. (4' methyl 3' aminobenzoyl) amino- 5-hydroxynaphthalene-7-su1fonic, acid,

2 (3' methyl 4' aminobe-nzoyl) amino- 5-hydroxynaphthalene-1,7-disulfonic acid, and

2 (4' methyl 3 aminobenzoyl) amino- 5-hydroxynaphthalene-1,7-disu1fonic acid,

and R3 represents the radical of an acyl derivative of one of the following amino-hydroxynaphthalene-sulfonic acid coupling components:

- @&

wherein R1 and R3 have the previously-indicated significances, X is H or SOsH, the CH3 group is in one of the positions 3 and 4 of the nucleus Y, and the N=NR3 group is in the other of these positions.

The new dyestufis dye cotton and regenerated cellulosein clear red to violet shades, the wash fastness' and light fastness properties of which are enhanced by after-treatment with metalyielding agents, such as copper sulfate; It is also possible to convert the new dyestuffs, in so far as their solubility will permit, in substance into light-fast, direct dyeing dyestuffs.

The copper complex compounds correspond to the following general formula wherein R4 is the radical of benzene or naphthalene position to the azo radical O or a compound of the series, a stands in orthogroup and represents the and wherein R3, X and Y have the previouslyindicated significances.

In the following illustrative examples, the parts are by weight and the temperatures are in degrees' Centigrade, The term "sod'a refers to sodium carbonate.

Example 1 18.9 parts of diazotized l-hydroxy-2-aminobenzenel-sulfonic acid are coupled with 3 1.2 parts of 2-('3-methyl-4-aminobenzoyl)-amino- 5 -'hydroxynaphth'alene-7-sulfonic acid in sodaalkaline medium, and the entire amount of ami-' noazo dyestuff thus obtained is stirred into 400 parts of water and, after addition of 7 parts of sodium nitrite, cooled to 8. At this temperature, 30 parts of concentrated hydrochloric acid are added and the mixture stirred until diazotization 1 is complete (about 2 hours). The obtaineddiazo suspension is run, at 5 -10", into a solution of 37.1 parts of 2-cinnamoylamino-5-hydroxynaphsoda in 500 parts of water. Couplingtakes place very rapidly. After 2 hours, the reaction mixture is heated to,70, the disazo dyestuff- -which has gone into solution-precipitated with 50 parts of sodium chloride, and the precipitated'dyestufi separated by filtration and dried at 90 in vacuo. [The new dyestuff thus obtained, which corresponds'to the formula HOsS - r I OHa v Example 2 13.8 parts of diazotized Z-aminobenzene-l-carboxylic acid are coupled with 37.2,.parts of 2- (3 -methy1-4 -aminobenzoyl) amino-fiehydroxynaphthalene-7-sulfonic acid in soda-alkaline medium, and the entire amount of aminoazo dyestufi thus obtained is stirred into 300 parts of water and, after addition of 7 parts of sodium nitrite,: cooled to 0. At this temperature, parts of concentrated hydrochloric acidla're-addp arts oif sodium 10 thalene-7-sulfonic acid and 40 parts of calcined,

ed and the mixture stirred until diazotization is complete (about 1 hour). The obtained diazo suspension is allowed to run, at 10, into a solution of 31.1 parts of 2-carbethoxyamino-5-hydroxynaphthalene-7-sulfonic acid and 40 parts of calcined soda in 400 parts of water. As soon as coupling is completed, the reactionmixtureis heated to the disazo dyestuff salted out with 'chl'oride, and the precipitated dyestuif separated by filtration and dried at 90 in vacuo.

The new dyestufi thus obtained, which corresponds to the formula is a 'red powder whichdissolves in water with blue-red coloration and dyes vegetable fibers/in red shades, the fastness to light and washing of the resultant dyeings being improved by aftercoppering.

nosm-Nno o oH cri Example 3 18.7 parts of diazotized Z-aminQnaphthaIene- 3-carboxylic acid are coupled with 37.2 parts of also be converted in sub 2 (3' -methyl-4'-'aminobenzoyl) a'mino 5 hydroxynap litlialene-7-sulfonic acid in soda-alkalin'e medium and the entire amount of am'inoazo dyestuff thus obtained is stirred into 300 parts of water and, after addition of 7 parts of sodium nitrite, cooled to 0. At this temperature 30 parts of concentrated hydrochloric acid are added and the mixture stirred until diazotization is complete (about 1 hour). The obtained diazo suspension is run, at 10 into a solution of 42.3 parts of 2-benzoylamino-5-hydroxynaphthalene- 1,7-disulfonic acid and 40 parts of calcined soda in 400 parts of water. As soon as coupling is completed, the reaction mixture is heated to 60, the disazodyestufi salted out with -50 parts of sodium chloride, and the precipitated dyestufi separatedby filtration -and dried at in vacuo.

. 8 The new dyestuff thus obtained, which correings turning toward the red-violet and become sponds to the formula ing fast to light and washing upon afteretreata ment with copper sulfate.

-COOH OH N=N on; on

HOaS NHQOO oas- NHGO is a red powder which dissolves in water with The said dyestufis can also be converted in blue-red coloration and dyes vegetable fibers in substance into a water-soluble copper complex red shades, the fastness to light and washing of which dyes vegetable fibres in red-violet shades the resultant dyeings being improved by afterwhich are very fast to light. coppering.

Example 4 Example 5 13.8 parts of diazotized 2-aminobenzene-1- 22.5 parts of diazotized 1-hydroxy-2-amino-6- chlorobenzenei-sulfonic acid are coupled with gf fi fi p g 6 1 37.2 parts of 2-(3-methyl-4'aminobenzoyl)- y ammo enzy ammo amino-5-hydroxynaphthalene-7-sulfonic acid in .droxynaphthalene'rl'Su1f9mc acld m Soda-Phalsoda-alkaline medium, and the entire amount of me medmm and t amotmt of ammoazo aminoazo dyestufi thus obtained is stirred into dyestufi thus obtamed. Stlrred Into 300 part? of 400 parts of water and, after addition of '7 parts a after adiiltmn of parts of sodmm of sodium nitrite, cooled to 8. At this temperamtnte' cooled to thls temgerattlre' ture, 30 parts of concentrated hydrochloric acid 30 parts of concentrated hydrochlonc acid are are added and the mixture stirred until diazotiadded and the mixture stirred 1mm diafzotizaizion zation is complete (about 2 hours). The obls 1 The q a mazo tamed diam Suspension is allowed to run at suspension 1s run at l 0, into a solution of 34.3 SL100, into a solution of parts of 4, parts of 2-benzoylamino-5-hydroxynapthalenea '7-sulfonic acid and 40 parts of calcined soda in zoylammobenzoyl) amino 5 hydroxynaptha- 1ene-l,7-disulfonic acid and parts of calcined 400 paws of Watel' As soon as couphng 15 pleted, the reaction mixture is heated to the 5 23; f g gg g g 3 52 5 12 351 2 3;? disazo dyestuff salted out with 50 parts of sodium ture is heated to the dissolved disazo dyestufi g if g a f g g, qyestufi Separated salted out with 50 parts of sodium chloride, and 40 i g a t gq the precipitated dyestuff separated by filtration 8 new yes ufi us ob amed 10 correand dried at in vacuo. sponds to the formula COOH The new dyestufi thus obtained which correis a red powder which dissolves in water with sponds to the formula blue-red coloration and dyes vegetable fibers in seen is a red-brown powder which dissolves in water red shades, the fastness to light and washing of with red coloration :and dyes cotton and ,regenthe resultant dyeings {being improved 1 byaf-tererated cellulose in red shades, the resultant dyecornering.

se 10 I The copper complex compounds of the dyeceding examples by equivalent quantities of the stuffs disclosed in the Examples 1 to 5 respecreactants set forth in the following tabular extively correspond to the following formulae: amples, and while otherwise proceeding as de- 0--Cu 0 N=N 0H, 0H Hols NH.OO N=N 03H 1108s -NHCOCH==OH 2. 0=o--'-0-- ou----o I N'= N CH; on

H028 --NH.CO- N= 1101s NELCOOCIH;

o l-O-Gu-O [I --N=--N OH: OH

Hols -N'H.CO N= Hols NH.CO

OaH O Q 4. OCu 0 I c1 =N CH5 011 H038 mrooO-ra v 0,11 Hols NH.CO V

I P I e N: CH; CH

110; -NH.CO-C N=N H038 NH.CO-O

.By replacing the reactants recited. in the prescribed, in the preceding exaniples, the correspending new disazo dyestuffs (see formulae of representative products, infra) are obtained:

Exam 16 Shade of after- No D Diazo compound of aminoazo dyestufi from Coupled with and component ccippcred yeing 6 2-amino-phenoxy-acetic acid 2-(3-methyl-4-aminobenzoyl)- 2 benzoylamino 5 hydroxy Red.

amino 5 hydroxy naphtha. naphthalene-7-sulfonic acid. lene-7-sulfonic acid.

7 do do 2- (2-carb0Xy-benzoy1) -amin- D0.

hydroxy naphthalene 7 sulfanic acid.

8 ..d0 2- (4-methyl-3-amin0benz0yl)- 2 benzoylamino 5 hydroxy 0.

amino -;5 hydroxy naphtha naphthalene-7-sulf0nic acid. Iene-7-sulf0nic acid.

9 3 amino naphthalene 2 car 2-(3'-methyl-4-aminobcnzoy1)- -.d0 D0.

boxylic acid. amino 5 hydroxy naphtha 1ene-7- sulfonic acid. 10 2 -a1 I(1iin0 benzene -1 carboxylic do do D0.

aci

11 do 2-(3-methyl-4-aminobenzoyl)- d0 D0.

amino-5-hydroxy-naphthalene-1,7-disu1f011ic acid.

12 .-d0 .do 2 (4 benzoy] aminobenzoyl) D0.

amino 5 hydrcxy naphtha le11c7su1fonic acid.

13 1-hydrog y-2 -am1no-bcnzene-4- do 2-benzoylamino-S-hydroxy- Red-vmlet.

sulfonic acid. naphthalene-7-sulionic acid.

14 1- hydroxy-2- amino- 6- chloro 2-(3-methyl-4'-aminobenz0yl) d0 Do.

benZcne-4-sulfonic acid. amino-5-hydroxy-naphthalene-7-sulionic acid. 15 .d0 .do Z-acetylamino-5-hydroxy-naphthalene-7-sulfonic acid. 16 1-hydroxy-2-ammo-benzenc-4- do d H Bordeaux.

sulfonic acid.

17 Z-aminobenzenc-i-carboxylic 2-(4-methyl-3-aminobenz0yl) 2-benzoylamino-5-hydr0xynaph- Redacid. amino-5-hydroxy-naphthathalene-7-sulf0nic acid.

2 '1ene-7-su1fonic acid.

18 d0 2-(3-m'ethyl-4"'aminobenz0yl)- 2 benz0ylamino-5-hydroxylue-red.

-5- Y r0 y-n ph naphthalene-1,7-disulfonic 1ene-7-sulfonic acid. acid.

19 ..do 0 2-(4 benzoyl aminobenzoyD- amino 5 hydroxy napthalenc-l, 7-disulf0nic acid.

0 .d .110 2 carbethoxy amino 5 by eddrpcy naphthalene 7 sulfom'c aci 21 1. hydroxy 2-amino benzene do do Bordeaux.

4-sulf0nic acid.

22 1-hydroxy-2-amino-benzenedo do DO.

4-sulfonic acid amide.

23 B-amino-napthalene 2 car- ,do Blue-red.

boxylic acid.

24 d0 .110 2 acetylamino 5 hydroxy napthalene-7-sulf0nic acid.

25 1 hydroxy 2 -amino benzene, d1 do Red-violet.

4-sulfonic acid.

26 2-aminobenzene-l-carboxylic acid do do Blue-red.

27 0 d0 2-(4 amino bcnzoyD-amino- 5 hydroxy napthalene 7 sulfonic acid.

28 .110 d0 2-(3-ami11obenzoyl)-amin0-5- 0- hydroxy-naphthalene7-su1- fcnic acid.

29 1-methoxy-2-amino-benzene-4- .do 2-(2'-carboxy-benz0yl)-amiI1o-5- R d.

sulfonic acid. hydroxy-naphthalene-7-sultonic acid. I 30 1-hydr0xy-2-amino-fi-chlorobendo d Red-Violet.

. zenc-4-sulfonic acid.

31 4-sulfamido-2-aminophenoxydo d Brownish-red.

acetic acid.

32 S-aminc-naphthalene -2-carbox- ..do do Blue-red.

ylic acid.

33 2-a1nno-benzene-l-carboxylic ..-do do 0- aci 34 .do ...d0 2-(2ch1oro-benzoy1)-amino-5- hydroxynaphthalene-7-sulionic acid.

35 "do -do z-cinnamoyl-amino-5-hydroxynaphthalene-7-sulfonic acid.

3 "do 1-benzoylan1ino-5-hydroxyo de xnaphtha1ene-7-sulionic acid.

37 l'hydroxy-zamino-benzene -4- d0 2-cinnamoy1amino-5-hydroxy- Red v ole sulfonic acid. naphthalene-7-sulf0nic acid.

38 do ..do l-benzoylamino 8 hydroxy naphthalene-c sulfonic acid.

39 l-hydroxy-Z-amino-6-chlor0bend0 do V olet.

zene-4-sulfonic acid.

40 3-aminonaphthalene-Z-carboxyld0 do l e-redic acid.

41 2-an nobenzenc-l-carboxylic d0 ac1 I 42 .do do 2-bcnz0ylamino-8-hydroxynaphthalcne-G-sulfonic acid.

3 l-hydroxy-Z-amincbcnzene-4-suld0 2-benz0y1amino-5-h y d r 0 x y ed vl et fonic acid-(4-hydr0xy-3-carnaphthalene-7-sulfonic acid. boxy-anilide) 44 do d0 2-bcnzoylamino-5-hyd roxy- D naphthalene-1,7-disulf0nic acid 45 do 2-(3-mcthyl-4-aminobcnzoyl)- 2-benz0y1amin0 5 h y d r o x y- D amino-5-hydroxy-naphthalencnaphthalene-7-sulfonic acid. 1,7-disultonic acid.

46 d0 i d0 Z-cinnamoyIamino-E-hydroxy- 'naphthalene-7-sulfonic acid. 47 2-amino-5-chloro-benzene-1- 2-(3-methyl-4-aminchenzoyl)- 2-benz0ylamino-5-hydr0xycarboxylic acid. amino-5-hydroxy-naphthalenm naphthalene-7-su1fonic acid.

' 7-su1f0nicIacid. 48 1-carboxy-2-amino-benzene-4-, do do sulfonic acid anilidc. 49 dc 2-(3-methyl-4-aminobenz0yl)- --do Blue-red.

' amino-Shydroxy-naphihalene- 1,7-disulfonic acid.

15 Having thus disclosed the invention, what is claimed is:

1. A disazo dyestufi which corresponds to the formula wherein R1 is the radical of a member selected from the group consisting of benzene and naphthalene compounds, Z stands for a substituent selected from the group consisting of -OH, OCH3, COOH and OCH2COOH and being linked to R1 in ortho-position to -azo-, R3 is the OH OH COOH Boss

OH: OH NH-o o-N=N I CH: OH NHC OAN=N HOsS 3. The disazo dyestufi' of the formula NH-C o 0 0,115

4. The disazo dyestufi of the formula COOH OH N=N CH OH Ho=s NHC 06.1w:

OaH

5. The disazo dyestufi' of the formula (IJHI NH-O OON=N 6. The disazo dyestufi of the formula OOQH 0H HOaS -co- HANS ISCHER.

UNITED STATES PATENTS REFERENCES CITED Number Name Date The following references are of record in the 5,950 Luther 1; 1 July 1, 1913 1,940,683 Jordan Dec. 26, 1933 file of this patent: 

1. A DISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 